JP4938035B2 - Composition for recording material containing diphenylsulfone crosslinking compound - Google Patents

Description

  The present invention relates to a composition for a recording material, which contains a diphenylsulfone crosslinking type compound and a monohydroxydiphenylsulfone derivative and has excellent image storage stability.

  Recording materials that use the color developed by the reaction between the color-forming dye and the developer can be recorded in a relatively simple device in a short time without complicated processing such as development and fixing. It is widely used for heat-sensitive recording paper for recording or pressure-sensitive copying paper for forms for copying several sheets simultaneously. These recording materials are required to develop colors quickly, maintain the whiteness of the non-colored portion (hereinafter referred to as “background”), and have a colored image and high fastness of the background. In recent years, it has come to be used in large quantities in fields in which the reliability of recorded images such as labels is important, and is used for plasticizers and oils and the like contained in organic polymer materials used for packaging and the like. There is a need for recording materials that exhibit high storage stability. For this purpose, efforts have been made to develop various auxiliaries such as color-forming dyes, developers, and storage stabilizers.

Among them, the inventors disclosed a diphenylsulfone cross-linked compound represented by the following formula (1), which is excellent in image plasticizer resistance, as a developer or an image storage stabilizer in Patent Document 1 and the like. Disclosed. The diphenylsulfone bridged compound represented by the formula (1) is also mixed with 4-hydroxy-4′-allyloxydiphenylsulfone, which is a known developer, as described in Patent Document 2. It is used.
However, it cannot be said that the diphenylsulfone crosslinking type compound represented by the formula (1) or a mixture with another developer has an ideal performance as a developer or an image storage stabilizer. It was.

WO97 / 16420 Publication JP 2006-175673 A

  Therefore, while pursuing improved performance as a recording material of the diphenylsulfone cross-linking compound represented by the formula (1), raw material 4, 4′- contained as an unreacted impurity in order to cope with environmental problems. It was also necessary to study to reduce bisphenol sulfone as much as possible.

  Under such circumstances, the inventors reacted 4,4′-bisphenolsulfone with a dihalide to form a diphenylsulfone bridged compound represented by the formula (1), and then a monohalogen such as allyl chloride. When a composition in which a compound was reacted and a part of the reaction product was precipitated from a solvent was used, a diphenylsulfone bridged compound represented by the conventional formula (1) and 4-hydroxy-4′-allyl were used. It has been found that it has superior performance compared with a mixture with oxydiphenyl sulfone, and the present invention has been completed.

〔式中、Ｘ及びＹは、各々相異なってもよく、直鎖または分枝状の炭素数１〜１２の飽和、不飽和あるいはエーテル結合を有する炭化水素基、または、

（Ｒはメチレン基またはエチレン基を表し、Ｔは水素原子またはＣ_１〜Ｃ_４のアルキル基を表す）を表す。Ｒ_１〜Ｒ_６はそれぞれ独立にハロゲン原子、Ｃ_１〜Ｃ_６のアルキル基またはＣ_２〜Ｃ_４アルケニル基を表す。またｍ，ｎ，ｐ，ｑ，ｒ，ｔは０〜４の整数を表し、２以上の時はＲ_１〜Ｒ_６は、それぞれ異なっていてもよい。ａは０〜１０の整数を表す。〕で表されるジフェニルスルホン架橋型化合物の少なくとも１種、及び
式（２）

（式中、Ｒ_７及びＲ_８はそれぞれ独立にハロゲン原子、Ｃ_１〜Ｃ_６のアルキル基またはＣ_２〜Ｃ_４アルケニル基を表す。Ｒ_９は、Ｃ_１〜Ｃ_６のアルキル基またはＣ_２〜Ｃ_４アルケニル基を表す。また、ｘ及びｙは０〜４の整数を表し、２以上の時はＲ_７及びＲ_８はそれぞれ異なっていてもよい。）で表されるモノヒドロキシジフェニルスルホン誘導体の少なくとも１種を含有する記録材料用組成物であって、前記式（２）で表されるモノヒドロキシジフェニルスルホン誘導体の少なくとも１種が、式（１）で表されるジフェニルスルホン架橋型化合物の少なくとも１種の存在下で、溶媒から析出させて得たものであることを特徴とする記録材料用組成物，
（Ｂ）式（３）

（式中、Ｒ_７、Ｒ_８、ｘ及びｙは式（２）の定義と同じ）で表されるジヒドロキシフェニルスルホン誘導体の含有量が１質量％以下であることを特徴とする（Ａ）に記載の記録材料用組成物、
（Ｃ）溶媒中で、式（３）で表されるジヒドロキシフェニルスルホン誘導体を式Ａ（Ｈａｌ）_２（式中、Ａは前記ＸまたはＹと同じ。ＨａｌはＣｌ、ＢｒまたはＩを表す。）で表されるジハロゲン化物と反応させて式（１）で表されるジフェニルスルホン架橋型化合物を生成させた後、式Ｒ_９−Ｈａｌ（式中、Ｒ_９はＣ_１〜Ｃ_６のアルキル基またはＣ_２〜Ｃ_４アルケニル基を、ＨａｌはＣｌ、ＢｒまたはＩを表す。）で表されるモノハロゲン化物を反応させ、さらに、反応生成物の一部を溶媒から析出させることを特徴とする（Ａ）に記載の記録材料用組成物の製造法，
（Ｄ）式（１）で表されるジフェニルスルホン架橋型化合物の少なくとも一種と式（３）で表されるジヒドロキシフェニルスルホン誘導体を含有する組成物と、式Ｒ_９−Ｈａｌで表されるモノハロゲン化物式を混合することにより、式（３）で表されるジヒドロキシフェニルスルホン誘導体を低減する方法、及び
（Ｅ）発色性染料を含有する記録材料において、上記（Ａ）又は（Ｂ）記載の記録材料用組成物を含有することを特徴とする記録材料に関する。That is, the present invention
(A) Formula (1)

[In the formula, X and Y may be different from each other, and are linear or branched hydrocarbon groups having 1 to 12 carbon atoms, saturated, unsaturated or ether bonds, or

(R represents a methylene group or an ethylene group, T is represents a hydrogen atom or an alkyl group C ₁ -C ₄₎ represents a. R _{1 to} R ₆ each independently represents a halogen atom, a C _{1 to} C ₆ alkyl group or a C _{2 to} C ₄ alkenyl group. M, n, p, q, r, and t represent integers of 0 to 4, and R _{2 to} R ₆ may be different from each other when the number is 2 or more. a represents an integer of 0 to 10. And at least one diphenylsulfone crosslinking compound represented by formula (2):

(In the formula, R ₇ and R ₈ each independently represent a halogen atom, a C ₁ -C ₆ alkyl group or a C ₂ -C ₄ alkenyl group. R ₉ is a C ₁ -C ₆ alkyl group or C _2. ~C represents a ₄ alkenyl group. Further, x and y represents an integer of 0 to 4, monohydroxy diphenyl sulfone derivative represented by the time of 2 or more may be different each R ₇ and R _8.) The composition for recording materials containing at least one of the above, wherein at least one monohydroxydiphenylsulfone derivative represented by the formula (2) is a diphenylsulfone crosslinked compound represented by the formula (1): A composition for recording material, which is obtained by precipitation from a solvent in the presence of at least one kind,
(B) Formula (3)

(Wherein R ₇ , R ₈ , x and y are as defined in formula (2)), the content of the dihydroxyphenyl sulfone derivative represented by (A) is 1% by mass or less The composition for a recording material according to the description,
(C) A dihydroxyphenylsulfone derivative represented by the formula (3) in the solvent is represented by the formula A (Hal) ₂ (wherein A is the same as X or Y. Hal represents Cl, Br or I). To form a diphenylsulfone bridged compound represented by the formula (1), and then a compound represented by the formula R ₉ -Hal (wherein R ₉ is a C ₁ -C ₆ alkyl group or (C ₂ -C ₄ alkenyl group, Hal represents Cl, Br or I)), and a part of the reaction product is precipitated from a solvent. A) The manufacturing method of the composition for recording materials as described in A),
(D) a composition containing at least one diphenylsulfone bridged compound represented by formula (1) and a dihydroxyphenylsulfone derivative represented by formula (3), and a monohalogen represented by formula R ₉ -Hal In the method for reducing the dihydroxyphenylsulfone derivative represented by the formula (3) by mixing a chemical formula and (E) a recording material containing a chromogenic dye, the recording according to the above (A) or (B) The present invention relates to a recording material containing a material composition.

The figure which shows the result of the thermal analysis of the reaction composition obtained by the synthesis example 1. FIG. The figure which shows the result of the thermal analysis of the powder mixture obtained in the comparative example 1. FIG. The figure which shows the analysis result of the X-ray diffraction of the reaction composition obtained by the synthesis example 1. FIG. The figure which shows the analysis result of the X-ray diffraction of the powder mixture obtained in the comparative example 1. The figure which shows the static sensitivity characteristic of the thermal recording paper produced in Example 1,2. FIG. 6 is a diagram showing dynamic sensitivity characteristics of the thermal recording paper created in Examples 1 and 2.

(1) Composition for recording material The composition for recording material of the present invention comprises at least one diphenylsulfone crosslinked compound represented by formula (1) and a monohydroxydiphenylsulfone derivative represented by formula (2). And at least one monohydroxydiphenylsulfone derivative represented by the formula (2) is contained in the presence of at least one diphenylsulfone bridged compound represented by the formula (1). It is obtained by precipitating from a solvent.
The precipitate is represented by the formula (3), a low molecular weight substance of the diphenylsulfone cross-linked compound represented by the formula (1), in addition to at least one monohydroxydiphenylsulfone derivative represented by the formula (2). This is presumed to be a mixed crystal containing a dihydroxyphenyl sulfone derivative or a disubstituted product thereof with a dihalide thereof.
Therefore, the composition for recording material of the present invention is a mixture of a precipitate that does not dissolve in a solvent such as a polymer of the diphenylsulfone cross-linking compound represented by the formula (1). Therefore, the mixture of the diphenylsulfone crosslinking type compound and the monohydroxydiphenylsulfone derivative described in JP-A-2006-175673 is a powder mixture and is different from the composition of the present invention.

The content of the diphenylsulfone cross-linking compound represented by the formula (1) in the recording material composition of the present invention is 50% by mass or more, and preferably 70 to 90% by mass. On the other hand, the content of the monohydroxydiphenylsulfone derivative represented by the formula (2) is 5 to 40% by mass, preferably 5 to 25% by mass.
The recording material composition of the present invention may contain a dihydroxyphenylsulfone derivative represented by the formula (3), but the content is 3% by mass or less, preferably 1% by mass or less. .

As a method for preparing the composition, a dihydroxyphenylsulfone derivative represented by the formula (3) is reacted with a dihalide represented by the formula A (Hal) ₂ in a solvent and represented by the formula (1). After the diphenylsulfone cross-linked compound is formed, a monohalide represented by the formula R ₉ -Hal is further added to adjust the temperature, pH, etc., thereby dihydroxyphenyl sulfone represented by the formula (3) One of the products containing the monohydroxydiphenylsulfone derivative represented by the formula (2) produced by reacting the derivative under conditions preferentially converting to the monohydroxydiphenylsulfone derivative represented by the formula (2). Part is deposited.
In the present invention, an unreacted dihydroxyphenylsulfone derivative represented by the formula (3) is mixed with a monohalide represented by the formula R ₉ -Hal to obtain the mono represented by the formula (2). Since it is converted into a hydroxydiphenylsulfone derivative, it can be reduced to 3% by mass or less, and further 1% by mass or less in the composition.

In carrying out the above method, the reaction with the monohalide represented by the formula R ₉ -Hal produces not only the monohydroxydiphenylsulfone derivative represented by the formula (2) but also other side reaction products, They may be used while containing them or may be used after being removed. As a by-product, the hydroxy group remaining in the diphenylsulfone bridged compound represented by the formula (1) or the dihydroxyphenylsulfone derivative represented by the formula (3) is substituted with R ₉ of R ₉ -Hal. Compound.

  The precipitation method from a solvent can be performed by a conventional method. For example, in the case of an aqueous solvent, an organic solvent such as an alcohol solvent such as methanol, ethanol, propyl alcohol or the like is added to obtain an organic solvent water mixed solution, the temperature is raised to 50 to 90 ° C., and an alkaline aqueous solution such as NaOH. To adjust the pH to 9-12. Then, an acid is added, it adjusts to pH 1-6, is stirred for 0 to 6 hours, and is crystallized. If necessary, cool to room temperature, filter, wash and dry.

(Diphenylsulfone cross-linked compound represented by formula (1))
The diphenylsulfone crosslinking type compound represented by the formula (1) used in the present invention will be described below. These diphenylsulfone crosslinking compounds may be used alone or as a mixture of two or more.

（Ｒはメチレン基またはエチレン基を表し、Ｔは水素原子またはＣ_１〜Ｃ_４のアルキル基を表す）を表す。Ｒ_１〜Ｒ_６はそれぞれ独立にハロゲン原子、Ｃ_１〜Ｃ_６のアルキル基またはＣ_２〜Ｃ_４アルケニル基を示す。またｍ，ｎ，ｐ，ｑ，ｒ，ｔは０〜４の整数を表し、２以上の時はＲ_１〜Ｒ_６は、それぞれ異なっていてもよい。ａは０〜１０の整数を表す。In the formula (1), X and Y may be different from each other, and are linear or branched hydrocarbon groups having 1 to 12 carbon atoms, saturated, unsaturated or ether bonds, or

(R represents a methylene group or an ethylene group, T is represents a hydrogen atom or an alkyl group C ₁ -C ₄₎ represents a. R _{1 to} R ₆ each independently represent a halogen atom, a C _{1 to} C ₆ alkyl group or a C _{2 to} C ₄ alkenyl group. M, n, p, q, r, and t represent integers of 0 to 4, and R _{2 to} R ₆ may be different from each other when the number is 2 or more. a represents an integer of 0 to 10.

Specific examples of the groups represented by X and Y include the following.
Methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, methylmethylene group, dimethylmethylene Group, methylethylene group, methyleneethylene group, ethylethylene group, 1,2-dimethylethylene group, 1-methyltrimethylene group, 1-methyltetramethylene group, 1,3-dimethyltrimethylene group, 1-ethyl-4 -Methyl-tetramethylene group, vinylene group, propenylene group, 2-butenylene group, ethynylene group, 2-butynylene group, 1-vinylethylene group, ethyleneoxyethylene group, tetramethyleneoxytetramethylene group, ethyleneoxyethyleneoxyethylene group , Ethylene oxide Methyleneoxyethylene group, 1,3-dioxane-5,5-bismethylene group, 1,2-xylyl group, 1,3-xylyl group, 1,4-xylyl group, 2-hydroxytrimethylene group, 2-hydroxy- 2-methyl trimethylene group, 2-hydroxy 2-ethyl trimethylene group, 2-hydroxy-2-propyl trimethylene group, 2-hydroxy-2-isopropyl trimethylene group, 2-hydroxy-2-butyl trimethylene group, etc. Is mentioned.

The alkyl group or alkenyl group of R _{1 to} R ₆ is a C _{1 to} C ₆ alkyl group or a C _{2 to} C ₄ alkenyl group, and specific examples thereof include a methyl group, an ethyl group, and an n-propyl group. , Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 1-methylpentyl group, 2 -Methylpentyl group, vinyl group, allyl group, isopropenyl group, 1-propenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 2-methyl-2-propenyl group and the like can be mentioned. The halogen atom represents chlorine, bromine, fluorine, or iodine.

Of the diphenylsulfone cross-linked compounds represented by the formula (1), a diphenyl sulfone cross-linked compound represented by the following formula (4) is preferable. Although the compound represented by Formula (4) may be used independently and may be used as a mixture, it is preferable to use as a mixture.

The diphenylsulfone bridged compound represented by the formula (1) is obtained by, for example, reacting a dihydroxyphenylsulfone derivative represented by the formula (3) with a dihalide represented by the formula A (Hal) ₂ in a solvent. Can be manufactured. In the formula of the dihalide represented by the formula A (Hal) ₂ , A is the same as X or Y, and Hal represents Cl, Br or I.
In detail, it can manufacture by the method as described in WO97 / 16420, for example.

  The reaction is preferably carried out in the presence of a basic substance in a two-layer system of an aqueous solvent or water and an organic solvent. In the reaction in a two-layer system of water and an organic solvent, for example, a benzene organic solvent such as benzene, toluene, chlorobenzene and dichlorobenzene, a ketone organic solvent such as diethyl ketone and methyl isobutyl ketone (MIBK), ethyl acetate and the like In a mixed solvent with an ester-based organic solvent, the reaction is carried out in the presence of an alkaline substance such as an alkali metal or alkaline earth metal hydroxide, specifically sodium hydroxide, potassium hydroxide or lithium hydroxide. The reaction is performed at a temperature of −20 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C. for several hours to several tens of hours. In the reaction with an aqueous solvent, the reaction is carried out in an aqueous solvent in the presence of the alkaline substance at a reaction temperature of 0 to 120 ° C. for several hours to tens of hours. After the reaction, a single compound with high purity can be obtained by selective extraction with a solvent.

  The butenyloxy type compound includes, for example, 4,4′-dihydroxydiphenylsulfone (BPS) and 1,4-dihalobutenes such as hydroxides of alkali metals and alkaline earth metals (for example, caustic soda, caustic potash, lithium hydroxide, etc.) or In the presence of their carbonates (sodium carbonate, potassium carbonate, lithium carbonate), etc., in aromatic solvents such as toluene, xylene, chlorobenzene, ketone solvents such as acetone, MIBK, etc., or these organic solvents and water It is obtained by reacting in a two-layer system.

  Examples of the alkylene bridged type compound include BPS and 1-bromo-4-chlorobutane, hydroxides of alkali metals and alkaline earth metals (for example, caustic soda, caustic potash, lithium hydroxide, etc.) or carbonates thereof (sodium carbonate, Reaction in an aromatic solvent such as toluene, xylene or chlorobenzene, a ketone solvent such as acetone or MIBK, or a two-layer system of these organic solvent and water in the presence of potassium carbonate or lithium carbonate). The product obtained by the above step and BPS are reacted in a solvent such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF), MIBK in the presence of alkali metal, alkaline earth metal or carbonate thereof. Obtained by.

  A particularly preferable composition is composed of a mixture containing two or more kinds different only in the value of a of the compound represented by the general formula (1). This production method is simple, and the content ratio of diphenylsulfone crosslinking compounds having different degrees of polymerization can be arbitrarily changed by changing the reaction ratio of the raw materials.

(Monohydroxydiphenylsulfone derivative represented by the formula (2))
The monohydroxydiphenyl sulfone derivative represented by the formula (2) used in the present invention will be described below.
These monohydroxydiphenylsulfone derivatives may be used alone or as a mixture of two or more.
In the formula (2), R ₇ and R ₈ each independently represent a halogen atom, a C _{1 to} C ₆ alkyl group or a C _{2 to} C ₄ alkenyl group. R ₉ represents an alkyl or alkenyl group of _C 2 -C ₄ of C1 -C6. Moreover, x and y represent the integer of 0-4, and when it is 2 or more, R ₇ and R ₈ may be different from each other.
R ₇ and _{R 8} are as defined for _R 1 to R ₆ in the formula (1) can be exemplified the same substituents. R ₉ is the same as defined for the C ₁ -C ₆ alkyl group or the C ₂ -C ₄ alkenyl group of R ₁ -R ₆ .
Specifically, 4-hydroxy-4′-allyloxydiphenyl sulfone, 4-hydroxy-4′-isopropyloxydiphenyl sulfone, 4-hydroxy-4′-n-propyloxydiphenyl sulfone, and the like are preferable.

The monohydroxydiphenyl sulfone derivative represented by the formula (2) is, for example, a dihydroxyphenyl sulfone derivative represented by the formula (3) R ₉ -Hal (wherein R ₉ is C _{1 to} C _{6 in} a solvent). Or a C ₂ -C ₄ alkenyl group is reacted with a monohalide represented by Hal represents Cl, Br, or I).
_{R 9} in R _{9 -Hal,} similarly to R 1 to R _6, an alkenyl group of the alkyl group or _C 2 -C ₄ of C 1 -C _6, can be exemplified the same substituents. An allyl group, an n-propyl group, and an iso-propyl group are preferable.

  As in the case of the diphenylsulfone cross-linking compound, the reaction is preferably performed in the presence of a basic substance in a two-layer system of an aqueous solvent or water and an organic solvent. In the reaction in a two-layer system of water and an organic solvent, for example, a benzene organic solvent such as benzene, toluene, chlorobenzene and dichlorobenzene, a ketone organic solvent such as diethyl ketone and methyl isobutyl ketone (MIBK), ethyl acetate and the like In a mixed solvent with an ester-based organic solvent, the reaction is carried out in the presence of an alkaline substance such as an alkali metal or alkaline earth metal hydroxide, specifically sodium hydroxide, potassium hydroxide or lithium hydroxide. The reaction is performed at a temperature of −20 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C. for several hours to several tens of hours. In the reaction with an aqueous solvent, the reaction is carried out in an aqueous solvent in the presence of the alkaline substance at a reaction temperature of 0 to 120 ° C. for several hours to tens of hours. After the reaction, a single compound with high purity can be obtained by selective extraction with a solvent.

(2) Recording material The composition of the present invention is useful as a recording material.
The composition of the present invention can be used for any application as long as it is a recording material using a chromogenic dye,
For example, it can be used for heat-sensitive recording materials or pressure-sensitive copying materials.
A method for producing a recording material containing a color-forming dye may be a generally used method. For example, in the case of use as an image storage stabilizer, other developing agents and sensitizers and other auxiliary agents When used as a developer, it is used together with various auxiliaries such as a sensitizer. Of course, it is also possible to combine the composition of the present invention and use one as an image storage stabilizer and the other as a developer. It is also possible to produce a recording material characterized by color development characteristics by using a compound having the same application as that of the composition of the present invention.

When the composition of the present invention is used for heat-sensitive recording paper, it may be carried out in the same manner as the known image storage stabilizer and developer, for example, the fine particles of the composition of the present invention and the coloring dye. It can be produced by mixing a suspension in which fine particles are dispersed in an aqueous solution of a water-soluble binder such as polyvinyl alcohol or cellulose, applying the mixture to a support such as paper, and drying.
When the composition of the present invention is used as an image storage stabilizer, it is used in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight, based on 1 part by weight of the color forming dye. In the case of being used as a developer, the ratio is 1 to 10 parts by weight, preferably 1.5 to 5 parts by weight, based on 1 part by weight of the color developing dye.

  In the above dispersion liquid, further other color developer, other image stabilizer, sensitizer, filler, dispersant, antioxidant, desensitizer, anti-tacking agent, antifoaming agent, light stabilizer, fluorescence enhancer A whitening agent etc. can be contained as needed. These chemicals may be contained in the coloring layer, but in the case of a multilayer structure, they may be contained in any layer such as a protective layer. In particular, when an overcoat layer or an undercoat layer is provided above and / or below the color forming layer, these layers can contain an antioxidant, a light stabilizer and the like. Furthermore, an antioxidant and a light stabilizer can be contained in these layers in the form of microcapsules if necessary.

  Examples of the chromogenic dye used in the recording material of the present invention include leuco dyes such as fluorane, phthalide, lactam, triphenylmethane, phenothiazine, and spiropyran, but are not limited thereto. Any color developing dye that develops color by contact with a developer that is an acidic substance can be used. In addition, these color-forming dyes are used alone to produce a recording material having the color to be developed, but two or more of them can be used in combination. For example, it is possible to produce a recording material that develops a true black color by using a mixture of red, blue, and green primary color developing dyes or black coloring dyes.

  Of these dyes, fluorane-based dyes are exemplified by 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3- (N -Ethyl-N-isobutylamino) -6-methyl-7-anilinofluorane, 3- (N-methyl-N-propylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl) -N-isopentylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-7- (o-chloroanilino) fluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3- (N -Ethyl-p-toluidino) -6-methyl-7-anilinofluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-dimethylamino-7- (m-trifluoromethylanilino) fluorane, 3- Dipentylamino-6-methyl-7-anilinofluorane, 3- (N-ethoxypropyl-N-ethylamino) -6-methyl-7-anilinofluorane, 3-dibutylamino-7- (o-fluoroanilino) ) Fluorane, 3-diethylaminobenzo [a] fluorane, 3-dimethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-5-methyl-7-dibenzylaminofluorane, 3-diethylamino-7-di Benzylaminofluorane, 3-diethylamino-5-chlorofluorane, 3-diethylamino-6- (N, N′-di Njiruamino) fluoran, 3,6-dimethoxy fluoran 2,4-dimethyl-6- (4-dimethylaminophenyl) include aminofluoran the like. Moreover, as a near-infrared absorbing dye, 3- (4- (4- (4-anilino) -anilino) anilino-6-methyl-7-chlorofluorane, 3,3-bis (2- (4-dimethyl) Aminophenyl) -2- (4-methoxyphenyl) vinyl) -4,5,6,7-tetrachlorophthalide, 3,6,6′-tris (dimethylamino) spiro [fluorene-9,3′-phthalide Other examples include 3,3-bis (4′-diethylaminophenyl) -6-diethylaminophthalide.

When the compound or composition of the present invention is used as an image storage stabilizer or when used in combination with another developer, a typical example of the developer of a thermal recording paper is bisphenol A, 4,4′-sec-butylidenebisphenol, 4,4′-cyclohexylidenebisphenol, 2,2-dimethyl-3,3-bis (4-hydroxyphenyl) butane, 2,2′-dihydroxydiphenyl, pentamethylene Bisphenol compounds such as bis (4-hydroxybenzoate), 2,2-dimethyl-3,3-di (4-hydroxyphenyl) pentane, 2,2-di (4-hydroxyphenyl) hexane, 4,4′- Dihydroxydiphenylthioether, 1,7-di (4-hydroxyphenylthio) -3,5-dioxaheptane, 2,2 ′ Sulfur-containing bisphenol compounds such as bis (4-hydroxyphenylthio) diethyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenylthioether, benzyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, 4-hydroxy Propyl benzoate, isopropyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, isobutyl 4-hydroxybenzoate, chlorobenzyl 4-hydroxybenzoate, methylbenzyl 4-hydroxybenzoate, diphenylmethyl 4-hydroxybenzoate, etc. 4-hydroxybenzoic acid esters, zinc benzoate, metal salts of benzoic acid such as 4-nitrobenzoic acid zinc, salicylic acids such as 4- (2- (4-methoxyphenyloxy) ethyloxy) salicylic acid, zinc salicylate, bis { 4- (Ouchi Oxycarbonylamino) -2-hydroxybenzoic acid} zinc salicylic acid metal salt such as zinc, 4,4′-dihydroxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-methyldiphenylsulfone, 4-hydroxy -4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-butoxydiphenylsulfone, 4,4'-dihydroxy-3,3'-diallyldiphenylsulfone, 3,4-dihydroxy-4'-methyldiphenylsulfone, 4 , 4′-dihydroxy-3,3 ′, 5,5′-tetrabromodiphenyl sulfone, etc., 4-hydroxyphthalate dimethyl, 4-hydroxyphthalate dicyclohexyl, 4-hydroxyphthalate diphenyl 4- Hydroxyphthalic acid diesters, 2- Esters of hydroxynaphthoic acid such as droxy-6-carboxynaphthalene, hydroxyacetophenone, p-phenylphenol, benzyl 4-hydroxyphenylacetate, p-benzylphenol, hydroquinone monobenzyl ether, and trihalo such as tribromomethylphenylsulfone Examples include methyl sulfones, sulfonylureas such as 4,4′-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane, tetracyanoquinodimethanes, 2,4-dihydroxy-2′-methoxybenzanilide, and the like. .
In addition, N- (2-hydroxyphenyl) -2-[(4-hydroxyphenyl) thio] acetamide, N- (4-hydroxyphenyl) -2-[(4-hydroxyphenyl) thio] acetamide or an equivalent amount thereof N- (4-methylphenylsulfonyl) -N ′-{3- (4-methylphenylsulfonyloxy) phenyl} urea, 4,4′-bis (3- (phenoxycarbonylamino) methylphenylureido) Diphenyl sulfone, 4-hydroxy-4′-n-propyloxydiphenyl sulfone, 4-hydroxy-4′-allyloxydiphenyl sulfone and the like can also be mentioned.

When the compound or composition of the present invention is used as a developer or in combination with another image storage stabilizer, typical examples of the image storage stabilizer for thermal recording paper are as follows. Epoxy group-containing diphenyl sulfones such as benzyloxy-4 ′-(2-methylglycidyloxy) -diphenylsulfone, 4,4′-diglycidyloxydiphenylsulfone, 1,4-diglycidyloxybenzene, 4- (α -(Hydroxymethyl) benzyloxy) -4'-hydroxydiphenylsulfone, 2-propanol derivatives, salicylic acid derivatives, metal salts of oxynaphthoic acid derivatives (especially zinc salts), 2,2-methylenebis (4,6-tert-butyl) Phenyl) phosphate metal salts and other water-insoluble zinc compounds. .

  Examples of the sensitizer include higher fatty acid amides such as stearamide, benzamide, stearic acid anilide, acetoacetanilide, thioacetanilide, dibenzyl oxalate, di (4-methylbenzyl) oxalate, and di (4-chlorooxalate). Benzyl), dimethyl phthalate, dimethyl terephthalate, dibenzyl terephthalate, dibenzyl isophthalate, bis (tert-butylphenol) s, diphenylsulfone and derivatives thereof, 4,4'-dihydroxydiphenylsulfone diethers, 2,4'- Dihydroxy diphenylsulfone diethers, 1,2-bis (phenoxy) ethane, 1,2-bis (4-methylphenoxy) ethane, 1,2-bis (3-methylphenoxy) ethane, 2-naphthol benzyl ether, diphenyl Min, carbazole, 2,3-di-m-tolylbutane, 4-benzylbiphenyl, 4,4′-dimethylbiphenyl, m-terphenyl, di-β-naphthylphenylenediamine, phenyl 1-hydroxy-naphthoate, 2- Naphthyl benzyl ether, 4-methylphenyl-biphenyl ether, 2,2-bis (3,4-dimethylphenyl) ethane, 2,3,5,6-tetramethyl-4'-methyldiphenylmethane, diphenyl carbonate, etc. Can do. Preferably, aromatics such as ethers such as 1,2-bis (3-methylphenoxy) ethane and 2-naphthylbenzyl ether, m-terphenyl, 4-benzylbiphenyl, di (4-methylbenzyl) oxalate, etc. There may be mentioned hydrocarbons. More preferred are diphenyl sulfone and derivatives thereof, particularly 4,4′-dihydroxydiphenyl sulfone diethers and 2,4′-dihydroxydiphenyl sulfone diethers, and 4,4′-dimethoxydiphenyl sulfone, 4,4 ′. -Diethoxydiphenylsulfone, 4,4'-dipropoxydiphenylsulfone, 4,4'-diisopropoxydiphenylsulfone, 4,4'-dibutoxydiphenylsulfone, 4,4'-diisobutoxydiphenylsulfone, 4,4 '-Dipentyloxydiphenylsulfone, 4,4'-dihexyloxydiphenylsulfone, 2,4'-dimethoxydiphenylsulfone, 2,4'-diethoxydiphenylsulfone, 2,4'-dipropoxydiphenylsulfone, 2,4' -Diiso Examples include lopoxydiphenylsulfone, 2,4′-dibutoxydiphenylsulfone, 2,4′-diisobutoxydiphenylsulfone, 2,4′-dipentyloxydiphenylsulfone, 2,4′-dihexyloxydiphenylsulfone, and the like. it can.

  As the filler, silica, clay, kaolin, calcined kaolin, talc, satin white, aluminum hydroxide, calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, barium sulfate, magnesium silicate, aluminum silicate, plastic pigment, and the like can be used. In particular, alkaline earth metal salts are preferred in the recording material of the present invention. Further, carbonates are preferable, and calcium carbonate, magnesium carbonate and the like are preferable. The use ratio of the filler is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight with respect to 1 part by weight of the coloring dye. It is also possible to use a mixture of the above other fillers.

  Examples of the dispersant include sulfosuccinic acid esters such as dioctyl sodium sulfosuccinate, sodium dodecylbenzene sulfonate, sodium salt of lauryl alcohol sulfate, fatty acid salt, and the like.

  Antioxidants include 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-propylmethylenebis ( 3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (2-tert-butyl-5-methylphenol), 1, 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 4- [4 -{1,1-bis (4-hydroxyphenyl) ethyl} -α, α-dimethylbenzyl] phenol and the like.

  Examples of the desensitizer include aliphatic higher alcohols, polyethylene glycol, and guanidine derivatives.

  Examples of the anti-sticking agent include stearic acid, zinc stearate, calcium stearate, carnauba wax, paraffin wax, ester wax and the like.

  Examples of the light stabilizer include salicylic acid-based UV absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy- 4-benzyloxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′- Benzophenone ultraviolet absorbers such as dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane, 2- (2′-hydroxy) 5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzo Triazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) ) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-5'-tert-o Tilphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-3′-dodecyl-5) '-Methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-undecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-undecyl-5'-methylphenyl) benzo Triazole, 2- (2′-hydroxy-3′-tridecyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tetradecyl-5′-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-pentadecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy) -3′-hexadecyl-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-4 ′-(2 ″ -ethylhexyl) oxyphenyl] benzotriazole, 2- [2′-hydroxy-4 ′-( 2 "-ethylheptyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4 '-(2" -ethyloctyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4'-(2 " -Propyloctyl) oxyphenyl] benzotriazole, 2- [2′-hydroxy-4 ′-(2 ″ -propylheptyl) oxyphenyl] benzotriazole, 2- [2′-hydroxy-4 ′-(2 ″ -propyl) Hexyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4 '-(1 "-ethylhexyl) o Xylphenyl] benzotriazole, 2- [2′-hydroxy-4 ′-(1 ″ -ethylheptyl) oxyphenyl] benzotriazole, 2- [2′-hydroxy-4 ′-(1′-ethyloctyl) oxyphenyl] Benzotriazole, 2- [2′-hydroxy-4 ′-(1 ″ -propyloctyl) oxyphenyl] benzotriazole, 2- [2′-hydroxy-4 ′-(1 ″ -propylheptyl) oxyphenyl] benzotriazole 2- [2′-hydroxy-4 ′-(1 ″ -propylhexyl) oxyphenyl] benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 (2H-benzotriazol-2-yl)] phenol, polyethylene glycol and methyl-3- [3-tert- Benzotriazole ultraviolet absorbers such as condensates with til-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate, Cyanoacrylate ultraviolet absorbers such as ethyl-2-cyano-3,3-diphenylacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, succinic acid-bis (2,2,6) , 6-Tetramethyl-4-piperidyl) ester, 2- (3,5-di-tert-butyl) malonic acid-bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester UV absorbers, 1,8-dihydroxy-2-acetyl-3-methyl-6-methoxynaphthalene and their association Or the like can be mentioned things.

The following can be illustrated as a fluorescent dye.
4,4′-bis [2-anilino-4- (2-hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2′-disulfonic acid = disodium salt 4,4 ′ -Bis [2-anilino-4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = disodium salt 4,4'-bis [2- Methoxy-4- (2-hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = disodium salt 4,4'-bis [2-methoxy-4- (2-Hydroxypropyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = disodium salt 4,4'-bis [2-m-sulfoanilino-4-bis Hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = disodium salt 4- [2-p-sulfoanilino-4-bis (hydroxyethyl) amino-1, 3,5-triazinyl-6-amino] -4 '-[2-m-sulfoanilino-4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfone Acid = tetrasodium salt 4,4′-bis [2-p-sulfoanilino-4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2′-disulfonic acid = four Sodium salt 4,4'-bis [2- (2,5-disulfoanilino) -4-phenoxyamino-1,3,5-triazinyl-6-amino] stilbene-2 2'-disulfonic acid = hexasodium salt 4,4'-bis [2- (2,5-disulfoanilino) -4- (p-methoxycarbonylphenoxy) amino-1,3,5-triazinyl-6-amino] stilbene -2,2'-disulfonic acid = hexasodium salt 4,4'-bis [2- (p-sulfophenoxy) -4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene -2,2'-disulfonic acid = tetrasodium salt 4,4'-bis [2- (2,5-disulfoanilino) -4-formalinylamino-1,3,5-triazinyl-6-amino] stilbene- 2,2′-disulfonic acid = hexasodium salt 4,4′-bis [2- (2,5-disulfoanilino) -4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6 -Amino] stilbene-2,2'-disulfonic acid = hexasodium salt

  When the composition of the present invention is used for pressure-sensitive copying paper, it can be produced in the same manner as in the case of using a known image storage stabilizer, developer or sensitizer. For example, a color forming dye microencapsulated by a known method is dispersed with an appropriate dispersant and applied to paper to produce a color forming sheet. Also, a developer dispersion is applied to paper to produce a developer sheet. At that time, when the compound of the present invention is used as an image storage stabilizer, it may be used by being dispersed in any dispersion of a color former sheet or a developer sheet. A pressure-sensitive copying paper is produced by combining the two sheets thus produced. The pressure-sensitive copying paper consists of an upper paper carrying and supporting a microcapsule containing an organic solvent solution of a chromophoric dye on the lower surface and a lower paper carrying and carrying a developer (acidic substance) on the upper surface. It may be a unit or a so-called self-content paper in which a microcapsule and a developer are applied on the same paper surface. As the developer used in this case or the developer used in combination with the compound of the present invention, those conventionally known are used, for example, acid clay, activated clay, apatite, bentonite, colloidal silica, aluminum silicate, silicic acid. Inorganic acidic substances such as magnesium, zinc silicate, tin silicate, calcined kaolin and talc, aliphatic carboxylic acids such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid and stearic acid, benzoic acid, p-tert-butylbenzoic acid Phthalic acid, gallic acid, salicylic acid, 3-isopropylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3-phenyl-5 (2,2-Dimethylbenzyl) salicylic acid, 3,5-di- (2-methylbenzyl) Aromatic carboxylic acids such as lithylic acid and 2-hydroxy-1-benzyl-3-naphthoic acid, metal salts of these aromatic carboxylic acids such as zinc, magnesium, aluminum and titanium, p-phenylphenol-formalin resin, p- Examples thereof include phenol resin developers such as butylphenol-acetylene resin, mixtures of these phenol resin developers and metal salts of the above aromatic carboxylic acids, and the like.

  Hereinafter, the recording material of the present invention will be described in detail with reference to examples, but the present invention is not necessarily limited thereto.

(Synthesis Example 1) Synthesis of Composition for Recording Material 29.0 g of water and 16.0 g of NaOH (0.40 mol) were added to a 1 L four-necked eggplant type flask equipped with a stirrer and a thermometer and dissolved by heating. To this was added 50.0 g (0.20 mol) of 4,4′-dihydroxydiphenylsulfone (hereinafter abbreviated as 4,4′-BPS). After heating up to 110 ° C., 14.3 g (0.10 mol) of bis (2-chloroethyl) ether (hereinafter abbreviated as DCEE) was added dropwise. After completion of the dropwise addition, the reaction was carried out for 6.5 hours while maintaining 110 ° C. After completion of the reaction, water and MeOH were added, and hydrochloric acid was added to the reaction solution to adjust pH. This reaction solution was subjected to high performance liquid chromatography (column: Mightysil RP-18 (manufactured by Kanto Chemical), mobile phase: CH ₃ CN / H ₂ O / 1% H ₃ PO ₄ = 640/360/5, UV wavelength: 260 nm). The results of analysis are shown in Table 1 below.

In the table, n = 1 to 7 represents a compound when n in the following formula (4) is 1 to 7.

  Next, the reaction solution was heated to 60 ° C., and while maintaining the pH at 7.4 with an aqueous NaOH solution, an appropriate amount of allyl chloride corresponding to the remaining 4,4′-BPS was added dropwise and reacted for 6 hours. The results of high performance liquid chromatography analysis of this reaction solution are shown in Table 2.

  In the table, BPS-MAE means 4-hydroxy-4'-allyloxydiphenylsulfone, and BPS-DAE means 4,4'-diallyloxydiphenylsulfone.

  Methanol 70mL was added to this reaction liquid, and it was set as 50% methanol aqueous solution. The temperature was raised to 70 ° C., and an aqueous NaOH solution was added to adjust the pH to 12.0. Further, water / methanol / hydrochloric acid (a solution containing 10% hydrochloric acid in water / methanol (volume ratio 1: 1)) was added dropwise to adjust the pH to 3.0, followed by stirring for 1 hour for crystallization. After allowing to cool to room temperature, filtration, washing with 120 mL of water / methanol (methanol content 44%) contained, and drying, 49.9 g of a white solid was obtained as a reaction composition. The results of high performance liquid chromatography analysis of this product are shown in Table 3 below.

(Comparative Example 1)
The compounds shown below were powder mixed at the following ratio to prepare a mixed composition. The results of high performance liquid chromatography analysis of this product are shown in Table 4 below.
Compound of formula (4): 43.3 g
・ 4-Hydroxy-4′-allyloxydiphenylsulfone: 5.2 g
・ 4,4′-diallyloxydiphenylsulfone: 1.5 g
Here, the compound of the formula (4) is a compound of the formula (4) produced in Synthesis Example 1, and is a mixture of n = 1 body to n = 7 body.

(Test Example 1) <Thermal analysis>
Each of the reaction composition of Synthesis Example 1 and the powder mixture composition of Comparative Example 1 was subjected to thermal analysis using a differential scanning calorimeter (DSC 8230 type, manufactured by Rigaku Corporation). The results are shown in (FIG. 1) and (FIG. 2).

(Test Example 2) <Powder X-ray diffraction>
Each of the reaction composition of Synthesis Example 1 and the powder mixture composition of Comparative Example 1 was analyzed using an X-ray diffraction apparatus JDX-8020 type (manufactured by JEOL Ltd.). The results are shown in (FIG. 3) and (FIG. 4).

Example 1 (Preparation of thermal recording paper)
・ Dye dispersion (liquid A)
3-di-n-butylamino-6-methyl-7-anilinofluorane 16 parts polyvinyl alcohol 10% aqueous solution 84 parts developer developer (liquid B)
Reaction composition of Synthesis Example 1 16 parts Polyvinyl alcohol 10% aqueous solution 84 parts Filler dispersion (liquid C)
Calcium carbonate 27.8 parts Polyvinyl alcohol 10% aqueous solution 26.2 parts Water 71 parts Firstly, each mixture of liquids A to C is sufficiently ground with a sand grinder, and each liquid dispersion of liquids A to C is dispersed. 1 part by mass of A liquid, 2 parts by mass of B liquid, and 4 parts by mass of C liquid were mixed to prepare a coating liquid. This coating liquid was applied to white paper using a wire rod (Webster, wire bar No. 12) and dried, and then subjected to a calendaring process to prepare a heat-sensitive recording paper (the coating amount was dry mass). About 5.5 g / m ² ).

Example 2 (Preparation of thermal recording paper)
Thermal paper according to the method described in Example 1 except that the powder mixture composition of Comparative Example 1 was used instead of the reaction composition of Synthesis Example 1 in the developer dispersion liquid (B solution) of Example 1. It was created.

(Test Example 3) <Thermal evaluation test-Color development characteristic test>
(Static color sensitivity)
The thermosensitive recording paper prepared in Examples 1 and 2 was subjected to static color development using a thermal tilt tester (manufactured by Toyo Seiki), and the print density was measured with a Macbeth reflection densitometer (RD-514, manufactured by Macbeth). did. The results are shown in FIG.
(Dynamic color sensitivity)
The thermal recording paper prepared in Examples 1 and 2 was dynamically colored using a thermal paper color test apparatus (TH-PMD type manufactured by Okura Electric Co., Ltd.), and the print density was measured with a Macbeth reflection densitometer. The results are shown in FIG.

The composition containing the diphenylsulfone cross-linking compound and the monohydroxydiphenylsulfone derivative of the present invention shows a specific pattern in which the results of thermal analysis and X-ray diffraction are different from those of the conventional powder mixture, and the color development sensitivity characteristics The Macbeth value at low temperatures is markedly improved over conventional powder mixtures. In addition, the sensitivity was improved as compared with the case of using a diphenylsulfone cross-linking compound alone, and the practical value as a developer or an image storage stabilizer was improved.
The present invention also removes the dihydroxyphenylsulfone derivative from the system by converting the dihydroxyphenylsulfone derivative used as a raw material of the diphenylsulfone cross-linking compound into a compound that can be used as a developer or an image storage stabilizer. Can be reduced.

Claims (5)

  Formula (3)

(Wherein R ₇ And R ₈ Each independently represents a halogen atom, C ₁ ~ C ₆ An alkyl group or C ₂ ~ C ₄ Represents an alkenyl group, x and y represent an integer of 0 to 4; ₇ And R ₈ May be different. ) And a dihydroxyphenylsulfone derivative represented by formula A (Hal) ₂ (In the formula, A represents X or Y in Formula (1), Hal represents Cl, Br, or I) and is reacted with a dihalide represented by Formula (1). After the formation of the cross-linked compound, the dihydroxyphenylsulfone derivative of formula (3) remaining as unreacted is further converted to formula R ₉ -Hal (wherein R ₉ Is C ₁ ~ C ₆ An alkyl group or C ₂ ~ C ₄ In the alkenyl group, Hal represents Cl, Br or I. ) Obtained by reacting a monohalide represented by formula (2)

(Wherein R ₇ , R ₈ , X and y are the same as defined in formula (3) and R ₉ Is C ₁ ~ C ₆ An alkyl group or C ₂ ~ C ₄ Represents an alkenyl group. The composition for recording materials containing the reaction composition obtained by precipitating the reaction product which contains the monohydroxy diphenyl sulfone derivative represented by this in the reaction system from the mixed solvent of alcohol solvent and water.
  Here, the diphenylsulfone cross-linked compound represented by the formula (1) represents the following compound.

[In the formula, X and Y may be different from each other, and are linear or branched hydrocarbon groups having 1 to 12 carbon atoms, saturated, unsaturated or ether bonds, or

(R represents a methylene group or ethylene group, T represents a hydrogen atom or C ₁ ~ C ₄ Represents an alkyl group. R ₁ ~ R ₆ Each independently represents a halogen atom, C ₁ ~ C ₆ An alkyl group or C ₂ ~ C ₄ Represents an alkenyl group. M, n, p, q, r, and t represent integers of 0 to 4; ₁ ~ R ₆ May be different from each other. a represents an integer of 0 to 10. ] The recording material composition according to claim 1, wherein the content of the dihydroxyphenylsulfone derivative represented by the formula (3 ) remaining in the reaction composition according to claim 1 is 3 % by mass or less. Formula (3)

(Wherein R ₇ and R ₈ each independently represent a halogen atom, a C _{1 to} C ₆ alkyl group or a C _{2 to} C ₄ alkenyl group, x and y represent an integer of 0 to 4 and 2 or more And R ₇ and R ₈ may be different from each other.) A dihydroxyphenyl sulfone derivative represented by formula A (Hal) ₂ (wherein A represents X or Y in formula (1), Hal Represents Cl, Br or I) to form a diphenylsulfone bridged compound represented by the formula (1) by reacting with a dihalide represented by the formula (1), and then remaining unreacted in the formula (3) The dihydroxyphenylsulfone derivative is further represented by the formula R ₉ -Hal (wherein R ₉ represents a C _{1 to} C ₆ alkyl group or a C _{2 to} C ₄ alkenyl group, and Hal represents Cl, Br, or I). Monohalogenated Formula (2) obtained by reacting the product

(Wherein R ₇ , R ₈ , x and y are as defined in formula (3), and R ₉ represents a C ₁ -C ₆ alkyl group or a C ₂ -C ₄ alkenyl group). The method for producing a reaction composition according to claim 1 or 2, wherein the reaction product containing the monohydroxydiphenylsulfone derivative is precipitated from a mixed solvent of an alcohol solvent and water .
Here, the diphenylsulfone cross-linked compound represented by the formula (1) represents the following compound.

[In the formula, X and Y may be different from each other, and are linear or branched hydrocarbon groups having 1 to 12 carbon atoms, saturated, unsaturated or ether bonds, or

(R represents a methylene group or an ethylene group, T is represents a hydrogen atom or an alkyl group C ₁ -C ₄₎ represents a. R _{1 to} R ₆ each independently represents a halogen atom, a C _{1 to} C ₆ alkyl group or a C _{2 to} C ₄ alkenyl group. M, n, p, q, r, and t represent integers of 0 to 4, and R _{2 to} R ₆ may be different from each other when the number is 2 or more . a represents an integer of 0 to 10. ] Formula (3)

(Wherein R ₇ and R ₈ each independently represent a halogen atom, a C _{1 to} C ₆ alkyl group or a C _{2 to} C ₄ alkenyl group, x and y represent an integer of 0 to 4 and 2 or more And R ₇ and R ₈ may be different from each other.) A dihydroxyphenyl sulfone derivative represented by formula A (Hal) ₂ (wherein A represents X or Y in formula (1), Hal Represents Cl, Br or I) to form a diphenylsulfone bridged compound represented by the formula (1) by reacting with a dihalide represented by the formula (1), and then remaining unreacted in the formula (3) The dihydroxyphenylsulfone derivative is further represented by the formula R ₉ -Hal (wherein R ₉ represents a C _{1 to} C ₆ alkyl group or a C _{2 to} C ₄ alkenyl group, and Hal represents Cl, Br, or I). Monohalogenated And the reaction product is precipitated from a mixed solvent of an alcohol solvent and water, and remains unreacted in the composition containing the diphenylsulfone cross-linking compound represented by the formula (1). A method of reducing the dihydroxyphenylsulfone derivative of formula (3) to 3% or less .
Here, the diphenylsulfone cross-linked compound represented by the formula (1) represents the following compound.

[In the formula, X and Y may be different from each other, and are linear or branched hydrocarbon groups having 1 to 12 carbon atoms, saturated, unsaturated or ether bonds, or

(R represents a methylene group or an ethylene group, T is represents a hydrogen atom or an alkyl group C ₁ -C ₄₎ represents a. R _{1 to} R ₆ each independently represents a halogen atom, a C _{1 to} C ₆ alkyl group or a C _{2 to} C ₄ alkenyl group. M, n, p, q, r, and t represent integers of 0 to 4, and R _{2 to} R ₆ may be different from each other when the number is 2 or more . a represents an integer of 0 to 10. ]   A recording material containing a coloring dye, comprising the composition for recording material according to claim 1.

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